CZ277495A3 - Synthetic layered material and its use in conversions of organic compounds - Google Patents

Abstract

This invention relates to a new synthetic layered material, a method for its preparation and use thereof as a sorbent and as a catalyst component in catalytic conversion of organic compounds.

Description

Field of technology

The present invention relates to a synthetic laminate, MCM-56, to a process for its preparation and to its use as a sorbent or catalyst component for the conversion of organic compounds.

Prior art

Porous inorganic substances have been found to be useful as catalyst and separation media for industrial applications. The opening of their microstructure allows the molecules to achieve relatively large specific surfaces in these materials, which increases their catalytic and sorption activity. The porous materials currently used can be classified into three categories using the details of their microstructure as the basis for classification. These categories are amorphous and paracrystalline carriers, crystalline molecular sieves and modified layered materials. Detailed differences in the microstructures of these materials themselves manifest both important differences in the catalytic and sorption behavior of the materials as well as differences in the various observable properties used to characterize them, such as their specific surface area, pore size and variability of these sizes, presence or absence of retngene diffraction patterns. diagrams and the appearance of materials when its microstructure is studied by transmission electron microscopy and electron diffraction methods.

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Amorphous and paracrystalline materials represent an important class of porous inorganic solids that have been used for many years in industrial applications. Typical examples of these materials are amorphous silicas commonly used in catalyst preparations and paracrystalline transition alumina. used as solid acid catalysts and catalyst supports for diesel reforming. The term amorphous as used herein refers to a material of small order range and can be somewhat misleading because almost all materials are arranged to the same degree, mostly on a local scale. An alternative term that has been used to describe these materials is indifferent to X-rays. The silica microstructure contains 100-250 Angstrom large particles of amorphous silica density (Kirk-Othmer Chemistry of Chemical Technology, 3rd ed. Vol. 20, John Wiley's Sons, New York, pp. 766-731, 1932), p. porosity resulting from gaps between particles. Because there is not a large extent of order in these materials, the pores tend to be distributed rather to a large extent, the loss of order is also itself manifested by an X-ray diffraction pattern, which is usually not significant.

Paracrystalline materials such as transition alumina also have a wide pore size distribution, but well-defined X-ray diffraction patterns usually contain several broad peaks. The microstructure of these materials contains small crystalline regions of condensed alumina phases and the porosity of these materials arises from irregular gaps between these regions. .Wefers and Chanakya Misra, Oxides and Hydroxides of Aluminum, Technical Paper No. 19 P.evised,

Alcoa Research Laboratories, pp. 54-59, 1987). Because, in the case of another material, there is no large range of order controlling the pore size in the material, the variability in pore size is typically too high. Pore sizes in these materials fall into a mode called the mesoporous range, including, for example, pores in the range of 15 to 200 Angstroms.

In sharp contrast to these structurally ill-defined solids are materials whose pore size distribution is very narrow because it is controlled by the precisely repeating crystalline nature of the material microstructure. For example, zeolites are ordered, porous crystalline materials, typically aluminosilicates, having a defined crystalline structure determined by X-ray diffraction, in which there are a large number of small cavities that can be interconnected by many smaller channels or faults. These cavities and pores are uniform in size in specific zeolitic materials. Because the dimensions of these disorders are such as to accommodate the adsorption of molecules of certain dimensions while repelling those that have larger dimensions, these materials are known as molecular sieves and are used in many ways to take advantage of these properties.

The prior art has led to the formation of many types of synthetic zeolites. Many of these zeolites have been labeled with a letter or other zeolites, as illustrated by zeolites A (U.S. Patent 2,882,243); X (US Patent 2882244); Y (U.S. Patent 3130007); ZK-5 (U.S. Patent 3,247,195); ZK-4 (US patent patent patent patent

3314752); ZSM-5 (US patent 37 02886); ^: Z5M-11 (US 3709979); ZSM-12 (US patent 3332449) , ZSM-20 (US 3972983); ZSM-35 (US patent 4016245) ; ZSM-23 (US 4076842); MCM-22 (US patent 4954325) ; MCM-35 (US

patent 4981663); MCM-49 (WO 92/22493) and PSH-3 (US Patent 4,439,409).

U.S. Pat. No. 4,439,409 relates to a crystalline molecular sieve composition called PSH-3 and its synthesis from a reaction mixture containing hexamethyleneimine, an organic compound which acts as a control agent for the synthesis of the present exposed MCM-56. The composition of the composition, which appears to be identical to PSH-3 of U.S. Patent 4,439,409 but to other structural components, is described in European Patent Publication No. 293032. Hexamethyleneimine is also intended for use in the synthesis of MCM-22 crystalline molecular sieves in U.S. Patent 4,954,325. ; MCM-35 in U.S. Patent 4,931,663; MCM-49 and WO 92/22493; and ZSM-12 in U.S. Patent 5,021,141. A molecular sieve composition designated as SSZ zeolite is disclosed in U.S. Patent 4,826,667 and European Patent Application No. 2,313,60, wherein said zeolite is synthesized from a reaction mixture containing adamantane quaternary ammonium ion.

Certain layered materials that contain layers capable of being interspersed with a swelling agent may be the basis for providing materials having a high degree of porosity. Examples of such layered materials include clays. Such clays can be swollen with water, with the clay layers being filled with water molecules. Other layered materials are not water swellable, but may be swollen by certain organic swelling agents such as. amines of a quaternary ammonium compound. Examples of such water-non-swellable layered materials are described in U.S. Patent 4,896,948 and include layered silicates, magadiite, kenyanite, trititanates and perovskites. Another example of a non-swellable layered material that can be swelled by certain organic swelling agents is a vacancy-containing titanometalate material described in U.S. Patent 4,831,006.

Once the laminate is swollen, the material can be reinforced by placing a thermally stable substance, such as silica, in the gaps between the layers. For example, U.S. Patent Nos. 4,331,006 and 4,859,643 describe methods for reinforcing non-swellable laminates described therein. Other patents describing the reinforcement of laminates and reinforced products include U.S. Patents 4,21188, 4,248,739, 4,776,090 and 4,367,163, and European Patent Application No. 205711.

The X-ray diffraction patterns of the reinforced layered materials can be of varying importance depending on the degree to which swelling and reinforcement interrupt the otherwise usually well-arranged layered microstructure. The regularity of the microstructure in some reinforced laminates is so poorly interrupted that only one peak is observed in the low angle region of the X-ray diffraction pattern at a d-distance corresponding to the interlayer repetition in the reinforced material. Less disturbed materials may show several peaks in this area, which are generally arranged for this basic repetition. The reflection of X-rays from the crystalline structure of the layers is also observed to some extent. The pore size distribution in these reinforced laminates is narrower than in amorphous and paracrystalline materials, but wider than in crystalline backbone materials.

The essence of the invention

The present invention is directed to a synthetic laminate, referred to herein as MCM-56, having a molar ratio composition

X ₂ O ₃ : (n) YO ₂ where n is less than about 35, X is a trivalent element and Y is a tetravalent element, wherein said material is further characterized by a sorption capacity for 1,3,5-trimethylbenzene of at least about 35 μΐ / gram of calcined synthetic material, an initial intake of 15 mg 2,2-dimethylbutane / gram of calcined synthetic material in less than about 20 seconds and an X-ray diffraction pattern for the calcined synthetic material having d-distance maxima of 12.4 ± 0.2, 9.9 ± 0.3 , 5.9 +. 0.1, 6.2 ± 0.1, 3.55 +. 0.07, and 3.42 +. 0.07 Angstrom.

The MCM-56 of the present invention is different from, but shows some similarities to, many crystalline backbone materials, namely MCM-22 and MCM-49, and certain other layered materials. MCM-56 has an average unit cell c-parameter of about 25.5 Angstroms without the formation of interlayer bridges. When the synthesized MCM-56 is calcined, for example, at 540 ° C, the structure does not condense but remains in a layered form. Calcined MCM-56 absorbs at least about 35 [mu] g / g of 1,3,5-trimethylbenzene, eg usually about 4 times more than 1,3,5-trimethylbenzene than calcined MCM-22 or MCM-49. Sorption data also distinguish calcined MCM-56 from calcined MCM-22 and MCM-49, with its rapid initial uptake of 2,2-dimethyibutane. MCM-56 has unique sorption and catalytic advantages over MCM. 22 and MCM49.

Specifically, the MCM-56 material of the invention appears to be substantially pure with small or undetectable crystalline or layered phase impurities and has an X-ray diffraction pattern that differs in combination of line positions and intensities from known synthesized or heat treated materials as shown below in Table I (synthesized) and Table II (calcined). In these tables, intensities are defined to the d-distance line at 12.4 Angstroms.

> M • q a in tn . tn t E I I tn '>> and u φ (tí u AND > G l S 3 3 ε > q. - ¹ C ~ Xl) Φ.-Q; i ε w ~> - Μ <n ?. 0 X T x: . - q , -j 2 X , x O. C X r-2. q tn • x- . Nd - o cxn'x tí-a-. : '> n Nd (d Φ - xq -q. x q Χ X X »í cůsd <· -of..· from £ 3 / .0) q TJ-τ'φ M- tn. CN O cn <3 · CN tn • r-í íi AND < '· • • in ti · - φ <d £> - AND CM X Ct it it it 1 -'E. ε C ¹ -q TJ rd X n x (d · X AJ C -q w > WITH tn > AND > M • - ¹ a E with ε ε 3 3 3 tn '> AJ 1 \ and fd aj φ > AJ «-Ι c Φ -q q tn q > X X X ‘ and others X.Q X q cn tn td > n Nd Ό o X CN cn Ό X 44 • rd «rd a a • • • r ~ CN LH in X —C n td φ n CM X I • • • • • • 3 X Φ r-d I—} v— *. rH rd X I O it it it X X • 1—, etc. ů 'id < you φ id q tj - E- < a ε Φ N

X> C> • q TJ j · i

x - C>

• q x (d x O H <TJ x • q

Yes

Φ

X

C • q 'tn i> I tn i i tn

El 3 3 3 E>

to tn i

X o

X ^ rd c χ q tn ^s id 'O cc id Φ' r — d Í-H

Q | Nd <q TJ - 'Φ M x> a • q TJ

CM X • O rd • O m • O X • O' r · O O ř » O O + l + l + l + l +! + l + l AND ct l cn CN X ... I -. | • • tn N ” CM cn VO it it • • rd n X

f 5 'cd

Ή 4J

C -H> N c

n <u <d U “· C φ -H H cn> w cn i

S 5 cn>

and cn

It s

and

Ή £ 3 O* n w ca 0 r-! c \ O 03 in T tí G -d φ 04 r-l • ♦ · · co \ o ό n n r— («—1 .--- ch ^ d <; W Ό - a> n > tí · L · ’- - r-ΐ r-l

Table II

Ή C > • H H i.e G 10 cn Jj Φ > cn > .at t 1 1 1 rH C ε i ε Φ • H

H cn> ε i i ε 3 cn>

<N

CNÍ

Σ

O

G -u

M W sd o tí c cd φ T * O WHAT cn 04 kO 04 i — 1 <—1 .— • 1 • • tn Oj tí < 04 r-i 1 1 co kO kO • • H Ό φ · M tí>> C • Η T3 rH r-í n n

and 1 1 CD 'ť *> u »Ή > c ·] • -C C J-> Φ cd n cn > r-4 Φ w C • H «3 - tf) CN T '-AND • with tí XJ O and w cn 2 \ d · 0 +1 C C

, ι I cn g I 3 cn £>

Cj \ d <CN w Ό - '«“ <

n> tj U>

1— ¹ • Η Ό

Γ * r- n r4 r-l O O • • • • • O O O O O +1 +1 +1 +1 +1 with l ι .. ο CN m 04 . | • tn p tí) O • • n n

The materials used to obtain the data in Table I were wet-baked layered MCM-56, wet-baked layered materials synthesized with the same organic control agent, which, when calcined, transformed into MCM-22 and wet-baked crystalline

-MCM-49. The materials used for the data in Table II were ·· the calcined materials used in Table I. The calcination of each material was in air at 540 ° C for 2 to 20 hours. The most effective diagnostic feature, allowing an initial distinction between MCM-56 and other members of this family (MCM-22 and MCM-49 type materials) is observed in the d-distance range of 8.8 to 11.2 Angstroms. The latter species show two separate maxima at approximately

8.3-9.2 Angstroms and 10.8-11.2 Angstroms with different depression between them. The MCM-56 is characterized by a wide band centered around a d-distance of 9.9 Angstroms. Although the band may have an asymmetric profile, for example with an inflection point, depression may be indicative of MCM-49 formation and loss of MCM-56.

These X-ray diffraction data were obtained with a Scintag diffraction system equipped with a germanium solid state detector using k-alpha medium radiation. Diffraction data were recorded by sequential scanning at 0.02 degrees two-theta, where theta is the Bragg angle and the time of 10 seconds is calculated for each degree. Interplanar distances d, were calculated in units. The angstrom (A) and the relative intensity of the lines, I / I _o is one hundredth of the intensity of the strongest line above the base, were obtained using the profile of a common routine (or the second perforated algorithm). Intensities are uncorrected for the Lorentz and polarization effects. Relative intensities are indicated by the symbols vs =. very strong (6 0-10U, s = strong (40 -60), m = medium (20 -40) and w = weak (0-20) It should be noted that the diffraction data reported for this sample as individual lines may contain multiple overlapping lines which, under certain conditions such as differences in crystallographic changes, may appear as split or partially split lines.Typically, crystallographic changes may include small changes in cell unit parameters and / or a change in crystal symmetry, without a change in These small effects, including changes in relative intensities, may also occur as a result of differences in cation content, skeletal composition, nature and degree of pore filling, and thermal and / or hydrothermal history. between materials, which is the case when comparing MCM-56 with similar materials, e.g. MCM-49, MCM-22 and PSH-3.

Significant differences in X-ray diffraction patterns of these materials can be explained by knowledge of the material structures. MCM-22 and PSH-3 are members of an unusual family of materials because, after calcination, there are changes in the X-ray diffraction patterns that can be explained by a significant change in one axial dimension. This indicates a profound change in the binding in the materials and not just a simple loss of the organic material used in the synthesis. The precursor members of this family can be clearly distinguished by X-ray diffraction from the calcined members (e.g., compare the middle columns in Tables I and II). Evaluation of the X-ray diffraction patterns of both the precursor and calcined forms shows many reflections with very similar position and intensity, while the other peaks are different. Some of these differences are directly related to the axial dimension and the bond.

Crystalline MCM-49 has an axial dimension similar to that of calcined family members and therefore there are similarities in their X-ray diffraction patterns.

Nevertheless, the MCM-49 axial dimension is different from that observed in calcined materials. For example, changes in axial dimensions in MCM-22 may be derived from peak positions that are particularly sensitive to these changes. Two such peaks appear at 1313.5

Angstroms and ~ 6.75 Angstroms in MCM-22 precursor, at 12.8 Angstroms and ~ 6.4 Angstroms in assynthesized MCM-49 and at ~ 12.6 Angstroms and ~ 6.30

Angstroms in calcined MCM-22. The ~ 12.8 Angstrom peak in MCM-49 is very close to the intense 12.4 peak

Angstrom observed for all three materials and often not fully separated from it. Similarly, a peak of ~ 12.6 Angstrom of calcined MCM-22 material is usually visible only * as an arm on an intense peak of ~ 12.3 Angstrom.

Other features that together distinguish MCM-56 from similar materials described above are summarized below in Table III.

Table III

Features MCM-22 as-synthesized: • layered swellable structure yes

MCM-49

3-dimensional no

MCM-56 layered yes condenses after calcination yes calcined: sorption capacity for 1,3,5-trimethylbenzene ¹ low yes no low high initial intake of 2,2-dimethylbutane ^ slow slow fast ^ Slow sorption capacity is defined as less than about 8 to 10 μΐ / g. High capacity is at least about 4 times low capacity. Calcined MCM-56 sorbs at least about 35 M / g.

The initial intake is defined as the time for adsorption of the first 15 mg of 2,2-dimethylbutane / gram of sorbent. Fast reception is less than 20 seconds; slow reception is at least 5 times greater than fast value.

One gram of calcined MCM-56 sorbs 15 mg of 2,2-dimethylbutane in less than about 20 seconds, eg, less than about 15 seconds.

The unique MCM-55 laminate of the present invention has a molar ratio composition

X ₂ O ₃ : (n) YO ₂ wherein X is a trivalent element such as aluminum, boron, iron and / or gallium, preferably aluminum; Y is a tetravalent element such as silicon and / or germanium, preferably silicon; and n is less than about 35, e.g., from 5 to less than about 25, usually from 10 to less than 20, more usually from 13 to 13. In as-synthesized form, the material has the formula, on an anhydrous basis and expressed in moles of oxide per n mol YO ₂ , as follows:

(0-2) M ₂ O: ί1-2) R: X ₂ O ₃ : (n) YO ₂ wherein M is an alkali metal or alkaline earth metal and R is an organic group. The M and R components are associated with the material as a result of their presence during the synthesis and are readily removed by post-synthesis methods, which are described in more detail below.

The MCM-56 material of the invention can be heat treated and in calcined form has a high specific surface area (greater than 300 m ₂ / g) and usually a large sorption capacity for certain large molecules compared to previously described materials such as calcined PSH-3, SSZ25 , MCM-22 and MCM-49. MCM-56 wet koiáČ, ie. as synthesized MCM-56, is swellable, indicating the absence of interlayer bridges, in contrast to MCM-49, which is non-swellable.

For expansion, the original alkali metal or alkaline earth metal cations, e.g., sodium, can be replaced, at least in part, by ion exchange with other cations in accordance with techniques well known in the art. Preferred replacement cations include metal ions, hydrogen ions, hydrogen precursors, e.g., ammonium ions, and mixtures thereof. Particularly preferred cations are those that modify the catalytic activity of certain hydrocarbon conversion reactions. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Table of the Elements.

When used as a catalyst, the MCM-56 material of the invention may be treated, normally by calcination, to remove some or all of the organic component. The crystalline material may also be used as a catalyst in close combination with a hydrogenation component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or a noble metal such as platinum or palladium if it is to have a hydrogenation-dehydrogenation function. Such a component can be introduced into the composition by cocrystallization, replacement with a Group IIIA element in the composition, e.g. aluminum, in the structure, impregnation with this element or intimate physical mixing with it. Such a component can be impregnated into or on, as in the case of platinum, by treating the silicate with a solution containing a platinum metal containing ion. Suitable platinum compounds for this purpose include chloroplatinic acid, platinum chloride and various compounds containing a platinum-amine complex.

MCM-56 can be heat treated without affecting its layered structure so that it is still swellable after heat treatment. The heat treatment is usually performed by heating to a temperature of at least about 370 ° C for at least 1 minute and generally no longer than 20 hours. Although sub-atmospheric pressure may be used in the heat treatment, atmospheric pressure is required for ease of use. The heat treatment can be performed at a temperature of up to about 925 ° C. The heat-treated product, especially in its metallic, hydrogen and ammonium forms, is particularly suitable for catalyzing certain organic, e.g. hydrocarbon, conversion reactions. Non-limiting examples of such reactions include those described in U.S. Patents 4,954,325, 4,973,784, 4,992,611; 4,956,514; 4,962,250; 4,982,033; 4,962,257;

4,962,256; 4,992,606; 4,954,663; 4,992,615; 4,983,276;

4,982,040; 4,962,239; 4,963,402; 5,000,839; 5,001,296;

4,986,394; 5,001,295; 5,001,283; 5,012,033; 5,019,670;

I 5,019,665; 5,019,664; and 5,013,422.

The layered MCM-56 material of the present invention, if used either as an adsorbent or as a catalyst in the organic compound conversion process, should be dehydrated, at least in part. This can be done by heating to a temperature in the range of 200 to 370 ° C in an atmosphere such as air, nitrogen, etc., and at atmospheric pressure, pressure below or above atmospheric pressure for between 10 minutes and 48 hours. Dehydration can also be performed at room temperature by placing the MCM-56 in a vacuum, but a long time is required to achieve sufficient dehydration.

The present layered MCM-56 material can be prepared from a reaction mixture containing sources of an alkali metal or alkaline earth metal (Μ) cation, e.g. sodium or potassium, a trivalent oxide X, e.g. aluminum, a tetravalent Y oxide, e.g. silicon, a control agent (R) and water, wherein said reaction mixture has a composition, in moles of oxide ratios, in the following ranges;

Reactants

YO ₂ / X ₂ O ₃ h ₂ o / yo ₂

OH '/ YO ₂

M / YO ₂ r / yo ₂ usable 5 to 3 5 10 to 70 0.05 to 0.5 0.05 to 3.0 0.1 to 1.0 preferably 10 to 25 16 to 40 0.06 to 0, 3 0.05 to 1.0 0.3 to 0.5

In the present synthetic method, the YO ₂ source should primarily comprise solid YO ₂ , for example at least about 30% by weight. solid YO ₂ to obtain the crystalline product of the invention. If YO ₂ is silica, use a source of silicon containing at least about 30 wt. solid silica, such as Ultrasil (precipitated, spray-dried silica, containing about 90% by weight of silica) or HiSil (precipitated hydrated SIO2, containing about 87% by weight of silica, about 6% by weight of H2O, and about 4%). 5% by weight of bound H 2 O from hydration and having a particle size of about 0.02 micrometers) facilitates the formation of crystalline MCM-56 from the above mixture under the necessary synthetic conditions. Therefore, preferably the YO2 source, e.g. silica, contains at least about 30 wt. of solid YO 2, e.g., silica, and more preferably at least about 40 wt. solid YO2, such as silica.

The control agent R is selected from the group consisting of cycloalkylamine, azocycloalkane, diazacycloalkane, and mixtures thereof, wherein the alkyl contains from 5 to 3 carbon atoms. Non-limiting examples of R include cyclopentylamine, cyclohexylamine, cycloheptylamine, hexamethyleneimine, heptamethyleneimine, nomcpiperazine, and combinations thereof.

The crystallization of the present layered material can be performed either in a static or stirred state in a suitable reaction vessel such as a polypropylene vessel or a Teflon liner or a stainless steel autoclave. The crystallization is preferably carried out at temperatures of 80 to 225 ° C. However, it is essential for the synthesis of MCM-56 from the above reaction mixture to terminate and interrupt the reaction before the onset of MCM-49 formation at the expense of MCM-56. The MCM-56 is then separated from the liquid and recovered. The time required for the synthesis of MCM-56 without subsequent conversion to MCM-49 will depend on the reaction temperature used. However, the reaction can be routinely controlled to allow interruption prior to the onset of MCM-49 formation by observing X-ray diffraction patterns in the d-distance range of 9-11 Angstroms as the reaction proceeds. at a d-distance of 9.9 +. 0.3, while MCM-49 shows 2 peaks centered at two distances of 9.0 and 11.2 Angstroms.

The layered MCM-56 material of the present invention can be used as an adsorbent to separate at least one component from a mixture of components in a vapor or liquid phase having different sorption characteristics relative to the MCM-56. Thus, at least one component may be partially or completely separated from a mixture of components having different sorption characteristics relative to MCM-56 by contacting the mixture with MCM-56 to selectively sorb one component.

The layered MCM-56 material of the invention can be used to catalyze many chemical conversion processes, including many industrially and commercially important processes. Examples of chemical conversion processes that are efficiently catalyzed by MCM-56, alone or in combination with one or more catalytically active substances, include either other crystalline catalysts, including those that require a catalyst with acidic activity. Specific examples include (1) alkylation of aromatic hydrocarbons, e.g., benzene, long chain olefins, e.g., C 1-4 olefin, under reaction conditions comprising a temperature of 340 ° C to 500 ° C, a pressure of 100 to 20,000 kPa (atmospheric to 200 atmospheres). ), a weight hourly space velocity of 2 h ^-1 to 2000 h ^-1 and a molar ratio of aromatic hydrocarbon / olefin of 1/1 to 20 μl to give long side chain aromatics which can subsequently be sulfonated to give synthetic detergents;

(2) alkylation of aromatic hydrocarbons with gaseous olefins to give short-chain aromatic compounds, e.g., alkylation of benzene with propylene to give cumene, under reaction conditions comprising a temperature of 10 ° C to 125 ° C, a pressure of 100 to 3000 kPa (1 to 30 atmospheres) and a mass hourly space velocity (WHSV) of 5 to 50 h ^-1 (3) alkylation of a reformate containing substantial amounts of benzene and toluenes and a fuel gas containing C ₅ olefins to give, inter alia, mono- and dialkylates under reaction conditions including a temperature of 315 ° C to 455 ° C, a pressure of 2860 to 5620 kPa and a WHSV-olefin of 0.4 to 0.8 h;

WHSV reformate 1 to 2 hours and gas recycle 1.5 to 2.5 v / v. supplied fuel gas;

(4) alkylation of aromatic hydrocarbons, e.g. benzene, toluene and naphthalene, long chain olefins, e.g.

^C 14 olefin, to give an alkylated aromatic lubricating base under reaction conditions comprising a temperature of 160 to 260 ° C and a pressure of 2510 to 3200 kPa;

(5) alkylation of phenols with olefins or alcohol equivalents to give long chain alkylphenols under reaction conditions comprising a temperature of 200 ° C to 250 ° C, a pressure of 1480 to 2110 kPa and a total WHSV of 2 to 10 h ^-3 ; and (6) alkylation isoalkane, e.g. isobutane, olefins, e.g. 2-butene, under reaction conditions comprising a temperature of -25 to 400 ° C, e.g. 75 to 200 ° C, pressure from atmospheric pressure to 3500 kPa, e.g. from 100 to 7000 kPa, weight hourly space velocity based on the olefin of 0.01 to 100 h ^'3 ·, e.g. from 0.1 to 20 h ^ - ^ - and the mole ratio of total isoalkane to total olefin of 1: 2 are 100: 1, e.g. CD3 : 1 to 30: 1.

For many catalysts, it is desirable to incorporate MCM-56 with other materials resistant to the temperatures and other conditions used in organic conversion processes. Such materials include active and non-active materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and / or metal oxides such as alumina. The latter may be naturally occurring or in the form of gelatinous precipitates or gels comprising mixtures of silica and metal oxides. The use of a material in conjunction with MCM-56, i.e., combined with or present during the synthesis of MCM-56, that is active tends to alter the conversion and / or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process, so that the products can be obtained economically and correctly without the use of other means to control the rate of the reaction. These materials can be incorporated into naturally occurring clays, such as bentonites and kaolin, to improve the resistance to catalyst breakage under normal operating conditions. The mentioned materials, ie. clays, oxides, etc., act as binders for catalysts. It is desirable to provide a catalyst having good resistance to breakage, as in normal use it is desirable to prevent the catalyst from disintegrating into pulverulent materials. These clay and / or oxide binders can normally only be used for the purpose of improving the catalyst breakage resistance;

Naturally occurring clays that may be in the new crystal composition include the montmorillonite and kaolin family, where this family includes subbentonites and kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which halloysite, kaolinite, dickite is the major component. , nacrite or anauxite. Such clays can be used in the raw state as they are originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders suitable for the composition with the present MCM-56 laminate also include inorganic oxides, especially alumina.

In addition to the above materials, MCM-56 may be in a composition with a porous matrix material such as silica-alumina, silica-magnesium oxide, silica-zirconia, silica-thorium dioxide, silica-beryllium oxide, silica titanium dioxide. as well as ternary compositions such as silica-alumina-thorium dioxide, silica-alumina-zirconia, silica-alumina manganese dioxide and silica-alumina-zirconia.

The relative proportions of finely divided MCM-56 material and inorganic oxide matrix can vary widely, with MCM-56 content ranging from 1 to 90% by weight and more usually, especially when the composite is prepared in the form of beads, ranging from 2 to 80%. by weight of composites.

The invention will now be described in more detail with reference to the examples and the accompanying figures.

Description of the figures in the accompanying drawings

Fig. 1 is an X-ray diffraction pattern of the dried product MCM-56 of Example 1.

Figure 2 is an X-ray diffraction pattern of the calcined MCM-56 product of Example 2.

Fig. 3 is an X-ray diffraction pattern of the dried product MCM-56 of Example 9.

Fig. 4 is an X-ray diffraction pattern of the calcined MCM-56 product of Example 10.

Fig. 5 (a) is an X-ray diffraction pattern of the product of Example 2.

Fig. 5 (b) is an X-ray diffraction pattern of the product of Example 3.

Fig. 5 (c) is an X-ray diffraction pattern of the product of Example 4.

Fig. 5 (d) is an X-ray diffraction pattern of the product of Example 5.

In the examples, when determining the alpha value, it should be noted that the alpha value is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst and provides a relative rate constant (rate of conversion of normal hexane to catalyst volume per unit time). It is based on the activity of a silica / alumina cracking catalyst, which is considered to be alpha 1 (rate constant = 0.016 s ^-1 ). The alpha assay is described in U.S. Patent 335,4078, Journal of Catalysis, No. 4, p. 527 (1965); No. 6, pp. 278 (1966) and No. 61, p. 395 (1980). The experimental conditions of the assay used herein include a constant temperature of 538 ° C and a variable flow rate as described in detail in Journal of Catalysis, no.

61, p. 395.

Examples of embodiments of the invention

Example 1

A mixture of 258 grams of water, 6 grams of 50% sodium hydroxide solution, 13.4 grams of sodium aluminate solution (25.5% Al ₂ O ₃ and 19.5% Na ₂ O), 51.4 grams of Ultrasil (VN3) and 27.1 grams of hexamethyleneimine (HMI) was reacted in a 60 ml stirred (400 rpm) autoclave at 143 ° C.

The reaction mixture had the following composition in mole ratios:

S1O2 / AI2O3 - 23

OH '/ SiO ₂ = 0.21

Na / SiO ₂ = 0.21

HMl / SiO ₂ = 0.35

H ₂ O / SiO ₂ = 20

The reaction is complete after 34 hours. The product was filtered off, washed with water to give a wet cake and dried in an oven at 110 ° C.

The wet cake portion of the product and the dried portion were subjected to X-ray analysis and were identified as MCM-56. The X-ray diffraction pattern of the dried MCM-56 is shown in Table IV and FIG. 1.

Table IV of Note ³

2 theta gave ^ 0 4.1 21.6 10 B 6.94 12.74 34 B, sh 7.15 12.36 100 WITH 8.9 9.9 32 WB 12.84 '6.89 12 B 13.89 6.38 7 VB, sh 14.32 6.18 15 WITH 15.92 5.57 8 WB 19.94 4.45 30 WB 21.98 4.04 43 B 22.51 3.95 59 VB 23.44 3.80 28 WB 24.97 3.57 43 WITH 25.93 3.44 100 WITH 26.61 3.35 51 3 31.52 2,833 th most common 5 WITH 33.40 2,683 th most common 10 WB 34.71 2,584 th most common 3 W3 36.26 2,477 th most common 3 WITH 37.00 2,429 th most common 3 WITH 37.75 2,333 th most common 9 WITH ^and S = sharp, B = broad, VB = very wide, WB = velm very wide, sh = shoulder Chemical composition of the product from the example 1 was, in wt.%,

N = 1.61

Na = 1.1

Al ₂ O ₃ ~ 6.6

S10 ₂ = 70.5 ash = 78.2

The SiO ₂ / Al ₂ O ₃ molar ratio in this was 13.

Arrived ?:

Example 2 A portion of the product of Example 1 was exchanged with ammonium ion by contact three times with 1M ammonium nitrate and then calcined in air for 6 h at 540 ° C. The X-ray diffraction pattern of the calcined product of this example appears to be MCM-56 and is shown below in Table V and Figure 2.

Table V of Note ³

2 theta dfA), ^ o 4.1 21.6 37 B 7.14 12.33 97 WITH '8.9 9.9 33 WB 12.30 6.92 12 B 14.42 6.14 59 WITH 15.80 5.61 14 WB 19.76 4.49 27 WB 22.45 3.96 73 WB 23.75 3.75 26 WB 25.10 3.55 37 WITH 26.05 3.42 100 WITH 26.79 3.33 35 B 31.75 2,318 th most common 6 WITH 33.52 2,673 th most common 10 WB 34.82 2,576 th most common 4 WB 36.44 2,466 th most common 3 WITH 37.9 6 2,370 th most common 6 with

^and S = sharp, B - wide, WB = very very wide

Example 3

For comparative purposes, Example 1 of U.S. Patent 4,954,325 was repeated. The as-synthesized crystalline material of the example, referred to herein as the MCM-22 precursor or MCM-22 precursor, was evaluated by X-ray diffraction analysis. The X-ray diffraction pattern is shown in Table VI and Figure 5 (b).

Table VI theta

3.1

3.9

6.53

7.14

7.94

9.67

12.85 13.26 14.3 6 14.70

15.85 i .L «J · w

’] 19.00

19.85

21.56 21.94 22.53 23.59 24.93 25.98

26.56 29.15 31.58

32.34 33.48 34.87

36.34 37.13 '37.82

28.5

22.7

13.53

12.38

11.13

9.15 6.89 6.68 6.17 6.03 5.59 4.67 4.47 4.12 4.05 3.95 3.77 3.56 3.43 3.36

3.06

2,833 th most common

2,768 th most common

2,676 th most common

2,573 th most common

2,472 th most common

2,413 th most common

2,379 <1

100

2

4 2

21 13

55 23

3 2

1 2 1 5

Example 4

The product of Example 3 was calcined at 538 ° C for 20 hours. The X-ray diffraction pattern of this calcined product is shown in Table VII below and in FIG. 5 (c).

and i

Table VII

2 theta gave IZX 2.80 31.55 25 4.02 21.93 10 7.10 12.45 96 7.95 11.12 47 10.00 3.85 51 12.90 6.86 11 14.34 6.18 42 14.72 6.02 15 15.90 5.57 20 17.81 4.98 5 19.08 4.65 2 20.20 4.40 20 20.91 4.25 5 21.59 4.12 20 21.92 4.06 13 22.67 3.92 30 23.70 3.75 13 25.01 3.56 20 26.00 3.43 100 26.96 3.31 14 27.75 3.21 15 28.52 3.13 10 29.01 3.08 5 29.71 3.01 5 31.61 2,830 th most common 5 32.21 2,779 th most common 5 33.35 2,687 th most common 5 34.61 2,592 th most common 5

Example 5

2.24 parts of 45% sodium aluminate are added to a solution containing 1.0 part of 50% NaOH solution and 43.0 parts of H 2 O in an autoclave. 8.57 parts of Ultrasil - precipitated silica - are added with stirring and then 4.51 parts of HMI.

The reaction mixture had the following composition, mol ratios

SiO ₂ / Al ₂ O ₃ = 23

OH '/ SiO ₂ = 0.21

Na / SiO ₂ = 0.21

HMI / SiO ₂ = 0.35

H ₂ O / SiO ₂ = 19.3

The mixture was crystallized at 150 ° ^C P ° ³⁴ with stirring. The product was identified as MCM-49 and had an X-ray pattern shown in Table VIII a na

Fig. 5 (d). The chemical composition of the product of Example 1 was, in wt.%, N = 1.61 On = 1.1 A1 ₂ O ₃ = 6.6 sio ₂ = 70.5 ash = 78.2 Molar the SiO ₂ / Al ₂ O ₃ ratio in this was 18. Sorption capacity, after calcination at 538 ° C for 9 h

were, in weight%, cyclohexane, 40 torr 10.0 n-hexane, 40 torr 13.1

H ₂ O, 12 torr 15.4

A portion of the sample was calcined in air for 3 hours at 538 ° C. this material shows the X-ray diffraction pattern shown in Table IX.

4JL.

Table VIII theta

3.1

3.9

6.81

7.04

7.89

9.80

12.76 13.42

13.92

14.22 14.63 15.81 17.71 18.86

19.23 20.09

20.93 21.44 21.74 22.16 22.56

23.53 24.83 .25.08

25.86

26.80

27.53 28.33 28.98 29.47 i 31.46 i 32.08 í 33.19

34.05

34.77 36.21 36.90 37.68

gave_ ^ o 28.5 18 22.8 7+ 12.99 61 sh 12.55 97 11.21 41 9.03 40 6.94 17 6.60 4 * 6.36 17 6.23 11 6.05 2 5.61 15 5.01 4 4.71 4 4.62 6 4.42 27 4.24 8 4.14 17 4.09 37 4.01 17 3.94 58 3.78 26 3.59 22 3.55 10 3.45 100 3.33 28 3.24 21 3.15 15 3.08 4 3.03 2 2,843 th most common 4 2,790 th most common 6 2,699 th most common 9 2,633 th most common 5 2,580 th most common 4 2,481 th most common 2 2,436 th most common 3 2,387 th most common 8

sh = arm + = non-crystalline MCM-49 peak * = Thanks to impurity ‘'

AND

Table IX

2-Theta

3.2

3.9

6.90

7.13

7.98

9.95

12.87

14.32 14.74

15.94

17.87 19.00

19.35 20.24 21.06 21.56 21.37

22.32

22.69

23.69 Í24.95

25.22

25.99

26.94 27.73 28.55 29.11 29.63 ί31.59 'i 32.23 ί 33.34

34.35 34.92

36.35 37.07 37.82

díAl I / I 28.0 9 + 22.8 7+ 12.81 48 12.39 100 11.08 46 8.89 53 6.88 10 6.18 36 6.01 11 5.56 17 4.96 2 4.67 5 4.59 3 4.39 .14 4.22 5 4.12 15 4.06 25 3.93 12 3.92 41 3.76 23 3.57 19 3.53 4 3.43 90 3.31 20 3.22 17 3.13 11 3.07 3 3.01 2 2,833 th most common 6 2,777 th most common 4 2,687 th most common 9 2,611 th most common 4 2,570 th most common 3 2,471 th most common 2 2,425 th most common 2 2,379 th most common 6

sh = arm + = non-crystalline MCM-49 peak

Example 6

The product of Example 2 was subjected to an alpha test to determine an alpha value of 106.

Example 7

To compare the microporosity and effective pore openings between MCM-56, MCM-22 and MCM-49, hydrocarbon compounds with increasing molecular dimensions were successively adsorbed on a portion of the calcined MCM-56, MCM-22 and MCM-49 products of the examples, by the procedure according to ELW, GRLandolt and AWChester in new Developments in Zeolite Science and Technology, Studies in Surface Science and Catalysis, 28, 547 (1986). The dynamic sorption results of this evaluation are shown in Table X below.

Table X

Sorbate MCM-56 MCM-22 MCM-49 μΐ / g with μΐ / g with μΐ / g with n-hexane 79 17 120 12 114 10 2,2-dimethyl- butane 69 12 72 252 85 233 1,3,5-trimethyl- benzene 41 24 8 550 do not negate

Sorption results represent a clear difference between the tested materials. MCM-56 has at least 4-fold the capacity of MCM-22 and MCM-49 for 1,3,5-trimethylbenzene, the most hindered molecule used in this evaluation. MCM-56 also demonstrates much faster initial sorption

2,2-dimethylbutane (time required for sorption of the first 15 mg 2,2-dimethylbutane / g sorbent at 30 torr 2,2-dimethylbutane in flowing helium at 373K) than MCM-22 or MCM-49. The corresponding times for representative MCM56, MCM-22 and MCM-49 materials were 12, 252 and 233 seconds. The initial rate of sorption of n-hexane is the time required to sorb the first 40 mg of n-hexane / g of sorbent and for 1,3,5-trimethylbenzene, the time required to sorb the first 7 mg

1,3,5-trimethylbenzene / g sorbent.

Example 8

Example 1 was repeated except that the reaction was complete after 40 h. X-ray analysis confirmed the product as MCM-56.

Example 9

A mixture of 258 grams of water, 20.5 grams of sodium aluminate solution (25.5% Al ₂ O ₃ and 19.5% Na ₂ O), 51.4 grams of Ultrasil (VN3) and 50 grams of hexamethyleneimine (HMI) is reacted in 600 ml stirred (400 rpm) autoclave at 154 ° C.

The reaction mixture had the following composition in mole ratios:

SiO ₂ / Al ₂ O ₃ = 15

OH '/ SiO ₂

Na / SiO ₂

HMl / SiO ₂ h ₂ o / sio ₂

0.17 0.17 0.66 x -: - rtC ·

The reaction is complete after 130 hours. The product was filtered, washed with water to give a wet cake and a portion was dried in an oven at 110 ^{O <Part} of the product wet cake and the dried portion was subjected to X-ray analysis and was -identifikována as MCM-56th The X-ray diffraction pattern of the dried MCM-56 is shown in Table XI and Figure 3.

Table XI theta notes ³

4.1

6.67

6.96

7.16

8.9

12.86

13.98

14.33

15.35

19.93 21.95 22.56 23.46

24.94

25.94 26.64

21.6

13.25

12.70

12.35 9.9 6.83 6.33 6.18 5.59 4.45 4.05 3.94 3.79 3.57 3.43

3.35

80 21

7

7

42

100

B, sh ^b

B

WITH

WB

VB, sh S

WB

WB

VB

B

WB

WITH

WITH

B í

i $ i

^and S = * sharp, B = wide, VB = * very wide, WB = very very wide, sh = shoulder

The chemical composition of the product of Example 9 was, in% by weight,

N

On

A1 ₂ O ₃

SiO ₂ ash = .1.42 - 2.3 = 9.3 = 70.3 »82.3

The S1O2 / Al2O3 molar ratio in this product was 13.

Example 10

A portion of the product of Example 9 was exchanged with ammonium ion by contact three times with 1M ammonium nitrate and then calcined in air for 3 h at 482 ° C, cooled to about 130 ° C and then calcined in air at 538 ° C. This material shows the X-ray diffraction pattern shown in Table XII and in FIG.

Table XII note ³ ·

2 theta dlAL 4.3 20.5 69 B 7.13 12.40 100 WITH 8.1 10.9 33 WB 9.8 9.0 37 WB 12.79 6.92 12 B 14.38 6.16 48 WITH 15.73 5.62 17 WB 19.74 4.50 24 WB 22.45 3.96 69 WB 23.70 3.75 23 WB 25.10 3.55 36 WITH 26.05 3.42 88 with 26.86 3.32 27 B 31.71 2,822 th most common 5 WITH 33.34 2,687 th most common 9 B 34.30 2,614 th most common 6 WB 36.40 2,463 th most common 5 WITH 37.92 2,373 th most common 5 WITH

^and S = sharp, B = wide, WB = very very wide

The X-ray diffraction patterns of the products of Examples 2 to 5 are shown in Figure 5. Figure 5 (a) is a diagram of the MCM-56 product of Example 2; Fig. 5 (b) is a diagram of the product of Example 3. The MCM-22 diagram of the product of Example 4 is shown in Fig. 5 (c) and the diagram in Fig. 5 (d) is of the MCM-49 product of Example 5. These diagrams are presented in this figure in a way that facilitates their comparison. Giant. 5 (b) and (c) are of as-synthesized layered material which is transformed into crystalline MCM-22 after calcination and crystalline MCM-22.

Claims (8)

PATENT CLAIMS Synthetic laminate having compositions expressed in molar relationship X ₂ O ₃ : (n) Y0 ₂ j where n is less than about 35, X is a trivalent element and Y is | a tetravalent element, wherein said material is further characterized by a sorption capacity for 1,3,5trimethylbenzene of at least about 35 μΐ / gram calcined synthetic material, an initial intake of 15 mg 2,2dimethylbutane / gram calcined synthetic material in less than about 20 seconds and an X-ray diffraction pattern for calcined synthetic material having maximum d-spacings of 12.4 ± 0.2, 9.9 ± 0.3, 6.9 ± 0.1, 6.2 and 0.1, 3.55 ± 0.07, and 3.42 ± 0.07 Angstroms, respectively. Synthetic material according to claim 1, wherein X is selected from aluminum, boron, iron and gallium and Y is selected from silicon and germanium. , The material of claim 1, wherein X comprises aluminum and Y 1 includes silicon. and The material of claim 1, wherein n is 5 to less than 25. The material of claim 6, wherein n is 10 to 20. .íKESGgi A material according to claim 1 having a composition, on an assynthesized, anhydrous basis and expressed in moles of oxides per n mol of Y ₂ , expressed by the formula (0-2) M ₂ O: (1-2) R: X ₂ O ₃ : ( n) Y0 ₂ wherein M is an alkali or alkaline earth metal and R is an organic group. The material of claim 6, wherein said R is selected from the group consisting of cycloalkylamine, azacycloalkane, diazacycloalkane and mixtures thereof, wherein the alkyl contains from 5 to 8 carbon atoms. 8. A process for converting a feedstock comprising organic compounds into conversion products comprising contacting said feedstock with a catalyst comprising the active form of the synthetic layered material of claim 1.